CN104862031A - Lubricating Oil Composition And Additive Therefor Having Improved Piston Deposit Control And Emulsion Stability - Google Patents

Lubricating Oil Composition And Additive Therefor Having Improved Piston Deposit Control And Emulsion Stability Download PDF

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CN104862031A
CN104862031A CN201510087022.0A CN201510087022A CN104862031A CN 104862031 A CN104862031 A CN 104862031A CN 201510087022 A CN201510087022 A CN 201510087022A CN 104862031 A CN104862031 A CN 104862031A
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compositions
acid
lubricant
alkyl
weight
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CN104862031B (en
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K.杨
W.Y.琳
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Afton Chemical Corp
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Afton Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Abstract

A lubricant additive composition, a method for reducing engine deposit formation and a method for improving emulsion stability of a lubricant composition. The lubricant additive composition includes (a) an organomolybdenum compound contributing from about 20 to no greater than 300 ppm by weight molybdenum to the lubricant composition based on a total weight of the lubricant composition containing the additive composition; (b) a boronated hydrocarbyl substituted succinimide dispersant; and (c) a reaction product of (i) a hydrocarbyl-dicarboxylic acid or anhydride, (ii) a polyamine, (iii) a dicarboxyl-containing fused aromatic compound, and (iv) a non-aromatic dicarboxylic acid or anhydride. The hydocarbyl group of the hydrocarbyl-dicarboxylic acid or anhydride has a number average molecular weight of greater than 1800 Daltons as determined by gel permeation chromatography. A weight ratio of (b) to (c) ranges from about 1:1 to about 4:1.

Description

The piston deposit with improvement controls and the lubricating oil composition of stability of emulsion and additive thereof
Technical field
The disclosure relates to lubricant compositions, especially for the improvement sediment monitoring characteristic of engine lubricant compositions and/or the additive of stability of emulsion character.
Background and general introduction
Usually some performance requriements specified in the specification that industry and/or original equipment manufacturers (OEM) assert must be met for the lubricating oil composition of engine oil application.Usually; engine oil must provide the oxidation of enough levels and abrasion protection, sludge and settling formation control, fuel economy benefit, with the consistency of sealing material and other physics expected and rheological properties of lubrication and suitability necessity, by various standardized engine and worktable measurements determination.Such as, ASTM Sequence IIIG tests is at ILSAC GF-4/API SM, ILSAC GF-5/API SN and GM dexos1 tMone of Engine Block Test required in specification, its minimum piston deposit (WPD) cleanliness factor index grade of weighing is respectively 3.5,4.0 and 4.5.Therefore, Continual Improvement WPD performance may be that engine oil reaches one of characteristic of many expectations of following specification.Similarly, may need to improve friction modifiers usage level to the expectation of the fuel economy performance of the enhancing of engine oil, known friction modifiers keeps the ability of stable emulsion to have negative impact to lubricant compositions, water and E85 fuel mix is measured by retaining in test in ASTM D7563 emulsion.
Therefore, still need the lubricant additive compositions improved, it can provide the stability of emulsion of the control of the piston deposit of improvement and improvement and be applicable to meet or exceed lubricant properties standard that is that propose at present and future.
About aforementioned, embodiment of the present disclosure provides a kind of lubricant additive compositions, the method for the method that formed for reducing engine deposits and stability of emulsion for improvement of lubricant compositions.Described lubricant additive compositions comprises (a) contributes about 50-about 300 ppm weight molybdenum organic molybdenum to lubricant compositions, based on the gross weight of the lubricant compositions containing compositions of additives; The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; (c) reaction product of (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides.The number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography.B the weight ratio of () and (c) is in about 1:1 extremely about 4:1 scope.
Another embodiment of the present disclosure provides a kind of method for the deposition of control piston within the engine.Described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and compositions of additives with lubricant viscosity, described lubricant additive compositions comprises: (a) contributes the organic molybdenum of about 50-about 300 ppm weight molybdenum, based on the gross weight of lubricant compositions to lubricant compositions; The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; (c) reaction product of (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides.The number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography.B the weight ratio of () and (c) is in about 1:1 extremely about 4:1 scope.
Another embodiment of the present disclosure provides a kind of for keeping the method for the stability of emulsion of engine lubricant compositions.Described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and lubricant additive compositions with lubricant viscosity, described lubricant additive compositions contains: (a) contributes the organic molybdenum of about 50-about 300 ppm weight molybdenum, based on the gross weight of lubricant compositions to lubricant compositions; The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; (c) reaction product of (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides.The number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography.B the weight ratio of () and (c) is in about 1:1 extremely about 4:1 scope.
The beyond thought advantage of the dispersant additives composition of disclosed embodiment is used to be, composition not only provides the engine deposits of improvement to control, it can also increase the friction modifiers containing metal, and can not adversely affect the stability of emulsion of lubricant compositions.
In order to clarify the implication of some term used herein, provide term to give a definition.
The term of the complete interchangeable of synonym thought in term used herein " oil compositions ", " lubricating composition ", " lubricating oil composition ", " lubricating oil ", " lubricant compositions ", " lubricating composition ", " lubricant compositions prepared completely " and " lubricant ", and the base oil referring to comprise primary amount adds the finished product lubrication product of the compositions of additives of minor amount.
The term of the complete interchangeable of synonym thought in term used herein " additive-package ", " multifunctional additive for lubricating oils " and " compositions of additives ", refer to that lubricating composition gets rid of the part of the feed of base oil mixture of primary amount.
Term used herein " hydrocarbyl substituent " or " alkyl " use with its common implication, and it is known to the skilled person.Particularly, it refers to have the carbon atom that is directly connected with the rest part of molecule and mainly has the group of hydrocarbon characteristic.The example of alkyl comprises:
(1) hydrocarbon substituent, namely, aliphatic series (such as, alkyl or alkenyl), alicyclic (such as, cycloalkyl, cycloalkenyl group) substituting group and aromatics replace, aliphatic series replaces and the aromatic substituent of alicyclic replacement and wherein completed the cyclic substituents (such as, two substituting groups form alicyclic group jointly) of ring by another part of molecule;
(2) hydrocarbon substituent replaced, namely, in the context of the present invention, substituting group containing non-hydrocarbon does not change main hydrocarbon substituent (such as, halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulphur oxygen base);
(3) assorted substituting group, namely, in the context of the present invention, although substituting group has main hydrocarbon characteristic, containing the atom beyond carbon in the ring be originally made up of carbon atom or chain.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group, such as pyridyl, furyl, thienyl and imidazolyl.Usually, for the carbon atom of every ten in alkyl, there are no more than two (such as, no more than one) substituents; Usually, in alkyl, substituents is not had.
Unless otherwise expressly noted, otherwise the component that term used herein " % by weight " guides accounts for the percentage ratio of the weight of whole composition.
Term used herein " oil soluble " or " dispersible " can but must not indicate described compound or additive is solvable, solubilized, miscible or can be suspended in oil with all proportions.But preceding terms does not mean that they are such as solvable or stably dispersible in oil, to being enough to the degree playing desired result in the environment adopting oil.In addition, if expected, the special additive that other additive also can allow to mix higher level is mixed in addition.
By adding one or more additives to prepare lubricating oil of the present disclosure, engine oil and/or crankcase oil in suitable base oil preparation, as detailed below.Additive can combine by additive-package (or enriched material) form and base oil, or, can combination single with base oil.The lubricant prepared completely, engine lubricant and/or crankcase lubricant can present the performance characteristics of improvement, based on the additive added and their corresponding proportion.
The present invention comprises following aspect:
1. a lubricant additive compositions, described composition comprises:
A () contributes about 20 to the organic molybdenum being not more than 300 ppm weight molybdenums, based on the gross weight of the lubricant compositions containing compositions of additives to lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
2. the compositions of additives of aspect 1, wherein component (iii) comprises 1,8-naphthalic anhydride.
3. the compositions of additives of aspect 1, wherein the hydrocarbyl substituent of component (b) is derived from the polyolefine of number-average molecular weight in about 1000-about 1600 dalton's scope, passes through gel permeation chromatography.
4. the compositions of additives of aspect 1, wherein every molar constituent (ii) is had an appointment the fused aromatic compounds reaction of 0.25-about 1.5 moles.
5. the compositions of additives of aspect 1, the lubricant compositions wherein containing additive comprises component (b) and (c) of about 0.5-about 5 % by weight.
6. the compositions of additives of aspect 1, wherein component (i) comprises succsinic acid or the acid anhydrides of polyalkenyl replacement.
7. the compositions of additives of aspect 6, wherein component (i) comprises polyisobutenyl succinic acid or acid anhydrides, and component (iii) comprises 1,8-naphthalic anhydride, and component (iv) comprises maleic anhydride.
8. the compositions of additives of aspect 7, wherein said polyisobutenyl is greater than the polyisobutene of 50 % by mole of terminal vinylidene content derived from having.
9. the compositions of additives of aspect 1, wherein every molar constituent (ii) is had an appointment component (iv) reaction of 0.25-about 1.5 moles.
10. a lubricant compositions, described composition comprises the compositions of additives of aspect 1.
11. the lubricant compositions of aspect 10, described composition also comprises one or more and is selected from following member: washing composition, non-metallic friction properties-correcting agent, antioxidant, rust-preventive agent, viscosity index improver, emulsifying agent, de-emulsifier, inhibiter, anti-wear agent, metal dialkyl phosphorodithioate, ashless amine phosphoric acid ester, defoamer and pour point reducer.
The lubricant compositions of 12. aspects 10, described composition also comprises oil soluble Ti-containing additive.
13. within the engine control piston deposition method, described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and lubricant additive compositions with lubricant viscosity, and described lubricant additive compositions comprises:
(a) to described lubricant compositions contribution about 20 to the organic molybdenum of molybdenum being not more than 300 ppm weight, based on the gross weight of described lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
The method of 14. aspects 13, wherein the hydrocarbyl substituent of component (b) is derived from the polyolefine of number-average molecular weight in about 1000-about 1600 dalton's scope, passes through gel permeation chromatography.
The method of 15. aspects 13, wherein component (c) (iii) comprises 1,8-naphthalic anhydride.
The method of 16. aspects 13, wherein component (c) (i) comprises maleic anhydride.
The method of 17. aspects 13, wherein said lubricant compositions comprises the dispersant additives composition of about 0.5-about 5 % by weight.
The method of 18. aspects 13, wherein component (c) (i) comprises polyisobutenyl succinic acid or acid anhydrides, and component (c) (ii) comprises the polyamine containing 3-5 nitrogen-atoms.
The method of 19. aspects 13, the mol ratio of the component (c) (iii) of wherein reacting with component (c) (i) and (c) (ii) is in about 0.25-about 1.5 scope, and the mol ratio of the component (c) (iv) of reacting with component (c) (i) and (c) (ii) is in about 0.25-about 1.5 scope.
20. the method for aspect 13, wherein said lubricant compositions also comprises one or more and is selected from following member: washing composition, dispersion agent, friction modifiers, antioxidant, rust-preventive agent, viscosity index improver, emulsifying agent, de-emulsifier, inhibiter, anti-wear agent, metal dialkyl phosphorodithioate, ashless amine phosphoric acid ester, defoamer and pour point reducer.
The method of 21. aspects 13, wherein said lubricant compositions also comprises oil soluble Ti-containing additive.
22. 1 kinds for keeping the method for the stability of emulsion of engine lubricant compositions, described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and lubricant additive compositions with lubricant viscosity, and described lubricant additive compositions comprises:
(a) to described lubricant compositions contribution about 20 to the organic molybdenum of molybdenum being not more than 300 ppm weight, based on the gross weight of described lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
The method of 23. aspects 22, wherein the alkyl of component (c) (i) comprises the polyisobutenyl derived from having the polyisobutene being greater than 50 % by mole of terminal vinylidene content.
Other details of the present disclosure and advantage part are stated in the description that follows, and/or learn by practice of the present disclosure.By the key element specifically noted in the dependent claims and combination, can realize and reach details of the present disclosure and advantage.
It should be understood that aforementioned summary description and following detailed description are all only exemplary and explanat, is not to limit claimed disclosure.
The description of exemplary
Aspect (comprising the various example of preparation and application of the present disclosure) now with regard to more restrictions of embodiment describes the disclosure.It should be understood that and present these embodiments only for illustration of object of the present invention, should not regard as and limit the scope of the invention.
Engine float chamber lubricant compositions is used for the vehicles containing spark ignition and compression ignition engine.Such engine can be used for the application of automobile, truck and/or train, and can based on including but not limited to that the fuel of gasoline, diesel oil, alcohol, compressed natural gas etc. operates.The disclosure can describe the lubricant being suitable as engine lubricant, such as, meet or more than the vehicle crankcase lubricant of ILSAC GF-5 and/or API CJ-4 lubricant level.
base oil
The base oil being applicable to prepare engine lubricant compositions can be selected from any suitable synthetic oil, animal oil, vegetables oil, mineral oil or their mixture.Animal oil and vegetables oil (such as, lard, Viscotrol C) and mineral lubricating oils can be used, the liquid petroleum of such as paraffinic hydrocarbons, naphthenic hydrocarbon or combination chain alkane-naphthene types and through solvent treatment or through acid-treated mineral lubricating oils.It is suitable that oil derived from coal or shale also can be.At 100 DEG C, basic oil viscosity can be about 2-about 15 cSt usually, or as another example, about 2-about 10 cSt.In addition, the oil derived from solution-air process is also suitable.
Suitable synthetic base oil can comprise alkyl ester, the poly-alpha-olefin of dicarboxylic acid, polyoxyethylene glycol and alcohol, comprises polybutene, alkylbenzene, the organic ester of phosphoric acid and silicone oil.Synthetic oil comprises that hydrocarbon ils is such as polymerized and poly-mutually alkene (such as, polybutene, polypropylene, propylene isobutylene copolymers etc.); Poly-(1-hexene), poly-(1-octene), poly-(1-decene) etc. and their mixture; Alkylbenzene (such as, dodecylbenzene, Tetradecylbenzene, dinonyl benzene, two-(2-ethylhexyl) benzene etc.); Polyphenylene (such as, biphenyl, terphenyl, alkylating polyphenylene etc.); Alkylating diphenyl ether and alkylating diphenylsulfide and their derivative, analogue and homologue etc.
Oxyalkylene polymer and interpretation and wherein terminal hydroxyl are by the spendable another kind of known synthetic oil of their derivative composition of the modification such as esterification, etherificate.Such oil is such as by making the oil of following polymerization preparation: the alkyl of ethylene oxide or propylene oxide, these polyoxyalkylene polymers and aryl ethers are (such as, the diphenyl ether that the methyl-polyisopropylene glycol ethers that molecular-weight average is about 1000, molecular weight are the polyoxyethylene glycol of about 500-1000, molecular weight are the Anaesthetie Ether etc. of the polypropylene glycol of about 1000-1500) or their list and polycarboxylate (such as, acetic ester, mixed C 3-C 8the C of fatty acid ester or tetraethylene-glycol 13oxo-acid diesters).
Spendable another kind of synthetic oil comprises dicarboxylic acid (such as, phthalic acid, succsinic acid, alkyl succinic acid, alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, alkenyl malonic etc.) with the ester of multiple alcohol (such as, butanols, hexanol, dodecyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol etc.).The specific examples of these esters comprise Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, fumaric acid di-n-hexyl ester, dioctyl sebacate, diisooctyl azelate, nonane diacid diiso decyl ester, dioctyl phthalate (DOP), didecyl phthalate, two (eicosane) ester of sebacic acid, linoleic acid dimer 2-ethylhexyl diester, react by the sebacic acid of 1 mole and the tetraethylene-glycol of 2 moles and the 2 ethyl hexanoic acid etc. of 2 moles the complex ester formed.
The ester that can be used as synthetic oil also comprises by C 5-C 12monocarboxylic acid and polyvalent alcohol and polyol ethers (such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol etc.) prepare those.
Therefore, can be used for preparing any base oil being appointed as I-V group in base oil optional comfortable American Petroleum Institute (API) (API) the base oil interchange guidelines of engine lubricant compositions described herein.Such base oil group is as follows:
Table 1
1i-III group is mineral oil basic material.
Base oil can containing poly-alpha-olefin (PAO) that is secondary or primary amount.Usually, poly-alpha-olefin is derived from the monomer with about 4-about 30 or about 4-about 20 or about 6-about 16 carbon atoms.The example of available PAO comprises derived from octene, decene, their those of mixture etc.At 100 DEG C, the viscosity of PAO can be about 2-about 15, or about 3-about 12, or about 4-about 8 cSt.The example of PAO be included in 4 cSt at 100 DEG C poly-alpha-olefin, at 100 DEG C the poly-alpha-olefin of 6 cSt, and their mixture.The mixture of mineral oil and aforementioned poly-alpha-olefin can be used.
Base oil can be the oil derived from Fiscber-Tropscb synthesis hydrocarbon.Use Fischer-Tropsch catalyst, by containing H 2fiscber-Tropscb synthesis hydrocarbon is prepared with the synthetic gas of CO.Such hydrocarbon needs further process usually, can be used as base oil.Such as, hydrocarbon can be used in U.S. Patent number 6,103,099 or 6, and 180, the hydroisomerization of method disclosed in 575; Be used in U.S. Patent number 4,943,672 or 6,096, the hydrocracking of method disclosed in 940 and hydroisomerization; Be used in U.S. Patent number 5,882, method disclosed in 505 dewaxes; Or be used in U.S. Patent number 6,013,171,6,080,301 or 6,165, the hydroisomerization of method disclosed in 949 and dewaxing.
The oil of unrefined, refining and the refining again of the openly natural or synthesis of type above (and two or more these mixtures any) can be used for base oil.Unrefined oil is for directly to be obtained by source that is natural or synthesis and without the need to being further purified those of process.Such as, the shale oil directly obtained by retorting operation, the oil directly obtained by primary distillation or directly to be obtained by esterification process and the ester oil used without the need to processing further is unrefined oil.Seemingly, difference is that they are further processed in one or more purification step, to improve one or more character for the oil of refining and unrefined oils.Many such purification techniques are well known by persons skilled in the art, such as solvent extraction, second distillation, acid or alkali extraction, filtration, diafiltration etc.By obtaining the oil of refining again with the method refining oil be applied to for serving like the oils for obtaining refining.The oil of refining more like this also referred to as rebuild or renovate or the oil of reprocessing, and usually to process in addition by relating to the technology of the additive of removing, pollutent and oil decomposition product.
Base oil can combine with compositions of additives disclosed in embodiment herein, to provide engine lubricant compositions.Therefore, base oil can the amount of about 50 % by weight-Yue 95 % by weight scopes be present in engine lubricant compositions, based on the gross weight of lubricant compositions.
dispersant additives composition
In the one side of disclosed embodiment, described method and composition comprises the dispersant additives composition using and comprise at least two kinds of alkyl dispersion agents.First alkyl dispersion agent is sour derived from hydrocarbyl succinic or the succinimide dispersants of the routine of acid anhydrides and amine.The succinimide dispersants of such routine can represent with following formula (I) and (II) and their mixture:
Wherein R 1for derived from the polyolefinic hydrocarbyl substituent of number-average molecular weight in about 1000-about 1600 dalton's scope, pass through gel permeation chromatography.Specially suitable hydrocarbyl substituent is derived from the polypropylene of number-average molecular weight in about 1200-about 1400 dalton's scope or the compound of polybutene.In one embodiment, R 1derived from having the polybutene being greater than 50 % by mole of terminal vinylidenes.R 2be selected from H ,-(CH 2) mh and ; R 3for ; And R 4be selected from hydrogen and-(CH 3), wherein m is the integer of 1-3 scope, and n is the integer of 1-10 scope.Method for the preparation of the conventional succinimide dispersants according to above formula is well known in the art and is described in such as U.S. Patent number 4,234,435 and 4,636,322.Such dispersion agent has the alkyl (R that about 1:1-is about 3:1 scope usually 1) with the mol ratio of dicarboxylic acid or anhydride moiety.Such dispersion agent is also by reacting by the method aftertreatment of routine with any various.In such post-treatment agent, the succinyl oxide having boron, urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon to replace, maleic anhydride, nitrile, epoxide, carbonate, cyclic carbonate salt, hindered phenolic ester and phosphorus compound.U.S. Patent number 7,645,726,7,214,649 and 8,048,831 is incorporated herein by reference.
The succinimide dispersants of specially suitable routine comprises the dispersion agent of boronation, its nitrogen content is in about 1 % by weight-Yue 2.5 % by weight scope, such as about 1.2 % by weight-Yue 2.0 % by weight, expect about 1.4 % by weight-Yue 1.7 % by weight, and the weight ratio of boron and nitrogen is about 1:1 scope at about 0.1:1-, such as about 0.2:1-is about 0.8:1, and particularly about 0.4:1-is about 0.55:1.
functionalized dispersion agent
Second dispersion agent of dispersant additives composition is functionalized dispersion agent.Functionalized dispersion agent is following reaction product: A) alkyl-dicarboxylic acid or acid anhydrides, B) polyamine, C) fused aromatic compounds containing dicarboxyl and D) non-aromatic dicarboxylic acid or acid anhydrides.Suitable functionalized dispersion agent is described in U.S. Publication No 2013/0040866, and it is incorporated herein by reference.
component A
Alkyl-the dicarboxylic acid of component A or the hydrocarbyl portion of acid anhydrides can derived from butene polymers, the polymkeric substance of such as iso-butylene.Suitable polyisobutene used herein comprises by having at least about 50 % by mole, such as about 60 % by mole, particularly the polyisobutene of about 70 % by mole of-Yue 90 % by mole and above terminal vinylidene content or highly reactive polyisobutenes formed those.Suitable polyisobutene can comprise use BF 3those of catalyst preparing.The substituent number-average molecular weight of polyalkenyl can change in wide region, such as about 100-about 5000, and such as about 500-about 5000, is measured by GPC, uses polystyrene as calibration reference, as mentioned above.
The dicarboxylic acid of component A or acid anhydrides can be selected from the carboxyl reaction thing beyond maleic anhydride or maleic anhydride, such as toxilic acid, fumaric acid, oxysuccinic acid, tartrate, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, ethylmaleic anhydride, dimethyl maleic anhydride, ethyl toxilic acid, dimethyl maleic acid, hexyl toxilic acid etc., comprise corresponding carboxylic acid halides and rudimentary aliphatic ester.Suitable dicarboxylic anhydride is maleic anhydride.For the preparation of in the reaction mixture of component A, the mol ratio of maleic anhydride and hydrocarbyl portion can wide variations.Therefore, mol ratio can be about 1:5 change at about 5:l-, and such as about 3:l-is about 1:3, and as another example, maleic anhydride can excessively use, and completes with driving a reaction.Unreacted maleic anhydride removes by vacuum distilling.
b component
In the dispersion agent that preparation is functionalized, any multiple polyamine can be used as B component.Non-restrictive illustrative polyamine can comprise aminoguanidine two carbonic ether (AGBC), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA) and heavy polyamine.Heavy polyamine can comprise the mixture of polyalkylene polyamine, it has a small amount of lower polyhydric amine oligomer such as TEPA and PEHA, but dominant oligomer has seven or more nitrogen-atoms, each molecule has two or more primary amine, and compared with the polyamine mixture greater amount branching of routine.The other non-limiting polyamine that can be used for the succinimide dispersants preparing alkyl-replacement is disclosed in U.S. Patent number 6,548,458, and its disclosure is attached to herein by reference and in full.In a kind of embodiment of the present disclosure, polyamine can be selected from tetren (TEPA).
In one embodiment, functionalized dispersion agent can derived from the compound of formula (I):
Wherein n represents the integer of 0 or 1-5, R 2for hydrocarbyl substituent as defined above.In one embodiment, n is 3 and R 2for polyisobutenyl substituting group, such as, derived from having at least about 50 % by mole, such as about 60 % by mole, the such as polyisobutene of about 70 % by mole of-Yue 90 % by mole and above terminal vinylidene content.The compound of formula (I) can be the succinyl oxide (such as polyisobutenyl succinic anhydride (PIBSA)) of alkyl-replacement and the reaction product of polyamine (such as tetren (TEPA)).
In compound, the succinyl oxide of (A) polyisobutenyl-replacement in the compound of previously described formula (I) and the mol ratio of (B) polyamine can be about 10:1 scope at about 1:1-.Dispersion agent available especially contains number-average molecular weight (Mn) and has general formula H in the polyisobutenyl of the succinyl oxide of the polyisobutenyl-replacement of about 500-5000 scope (using polystyrene to measure as calibration reference by GPC) with (B) 2n (CH 2) m-[NH (CH 2) m] n-NH 2polyamine, wherein m in 2-4 scope and n in 1-2 scope.
component C
Component C is carboxyl or polycarboxylic acid or multi-anhydride, and wherein carboxylic acid or anhydride functional group and aromatic group directly condense.The aromatic substance containing carboxyl like this can be selected from 1,8-naphthalic acid or acid anhydrides and 1,2-naphthalic acid or acid anhydrides, 2,3-dioctyl phthalate or acid anhydrides, naphthalene-1,4-dioctyl phthalate, naphthalene-2,6-dioctyl phthalate, Tetra hydro Phthalic anhydride, PMA, 1,2,4-benzene tricarboxylic acid acid anhydride, biphenyl dicarboxylic acid or acid anhydrides, 2,3-dinicotinic acid or acid anhydrides, 3,4-dinicotinic acid or acid anhydrides, Isosorbide-5-Nitrae, 58-naphthalenetetracarbacidic acidic or acid anhydrides, -3,4,9,10-tetracarboxylic acid anhydrides, pyrene dioctyl phthalate or acid anhydrides etc.Mole number/B component the mole number of the component C of reaction can be about 2:1 scope at about 0.1:1-.The typical mol ratio of component C and B component can be about 2.0:1 scope at about 0.2:1-in the reactive mixture.Another mol ratio of spendable component C and B component can be about 1.5:1 scope at 0.25:1-.Component C can at the temperature of about 140 DEG C of-Yue 180 DEG C of scopes with other component reaction.
component D
Component D is non-aromatic carboxylic acid or acid anhydrides.Suitable carboxylic acid or its acid anhydrides can include but not limited to acetic acid or acid anhydrides, oxalic acid and acid anhydrides, propanedioic acid and acid anhydrides, succsinic acid and acid anhydrides, alkenyl succinic acid or acid anhydrides, pentanedioic acid and acid anhydrides, hexanodioic acid and acid anhydrides, pimelic acid and acid anhydrides, suberic acid and acid anhydrides, nonane diacid and acid anhydrides, sebacic acid and acid anhydrides, toxilic acid and acid anhydrides, fumaric acid and acid anhydrides, tartrate or acid anhydrides, glycol acid or acid anhydrides, 1,2,3,6-naphthane dioctyl phthalate or acid anhydrides etc.The mol ratio of the component D reacted with B component is in the B component scope of the reaction of about 0.1-about 2.5 molar constituent D/ mole.Usually, the amount of component D used is relative to the quantity of secondary amino group in B component.Therefore, the secondary amino group in about 0.2-about 2.0 molar constituent D/ B component can with other component reaction, to provide the dispersion agent according to embodiment of the present disclosure.Another mol ratio of spendable component D and B component can be about 1.5:1 molar constituent D/ molar constituent B scope at 0.25:1-.Component D can at the temperature of about 140 DEG C of-Yue 180 DEG C of scopes with other component reaction.
Dispersant additives composition can contain mixture of dispersing agents, and wherein (b) is about 4:1 scope with the weight ratio of (c) at about 1:1-, and such as about 1.5:1-is about 3:1, and particularly about 1.8:1-is about 2.2:1.Therefore, lubricant compositions described herein can containing the above-mentioned dispersant additives composition of the 0.5 % by weight-Yue 10.0 % by weight that has an appointment, based on the gross weight of lubricant compositions.The typical range of dispersant additives composition can be about 2 % by weight-Yue 6 % by weight, based on the gross weight of lubricant compositions.Except foregoing dispersant compositions of additives, lubricant compositions also can comprise the composition of other routine, includes but not limited to friction modifiers, metal detergent, anti-wear agent, defoamer, antioxidant, viscosity modifier, pour point reducer, inhibiter etc.
washing composition containing metal
The metal detergent that can use together with above-mentioned dispersant reaction product comprises the polar head with long hydrophobic tail usually, and wherein polar head comprises the metal-salt of acidic organic compound.Salt can contain the metal of stoichiometry substantially, and in this case, they are described as standard or neutral salt usually, and total basicnumber or TBN (being measured by ASTM D2896) are less than about 150 for about 0-usually.Reacted by excessive metallic compound (such as oxide compound or oxyhydroxide) and sour gas (such as carbonic acid gas), a large amount of metal base can be comprised.The overbased detergent obtained comprises the micella of the neutralisation washing composition of the core around inorganic metal alkali (such as, hydrated carbonate).The TBN of such overbased detergent can be about 150 or larger, such as about 150-about 450 or larger.
The washing composition being applicable to the present embodiment comprises oil soluble high alkalinity, low alkali and the neutral sulfonate of metal (particularly basic metal or alkaline-earth metal, such as sodium, potassium, lithium, calcium and magnesium), phenolate, the phenolate of sulfuration and salicylate.Can exist more than a kind of metal, such as, both calcium and magnesium.It is suitable that the mixture of calcium and/or magnesium and sodium also can be.Suitable metal detergent can be high alkalinity calcium that TBN is 150-450 TBN or magnesium sulfonate, TBN is the high alkalinity calcium of 150-300 TBN or the phenolate of magnesium phenolate or sulfuration and TBN are high alkalinity calcium or the magnesium salicylate of 130-350.Also can use the mixture of such salt.
Washing composition containing metal can the amount of about 0.5 % by weight-Yue 5 % by weight be present in lubricating composition.As another example, the washing composition containing metal can about 1.0 % by weight-Yue 3.0 % by weight amount exist.Washing composition containing metal can be enough to for lubricant compositions provides the amount of about 500-about 5000 ppm basic metal and/or alkaline-earth metal to be present in lubricating composition, based on the gross weight of lubricant compositions.As another example, the washing composition containing metal can be enough to provide the amount of about 1000-about 3000 ppm basic metal and/or alkaline-earth metal to be present in lubricating composition.
based on the anti-wear agent of phosphorus
The wear preventative based on phosphorus can be used, and metal dialkyl phosphorodithioate compound can be comprised, such as but not limited to dialkyldisulfide for zinc phosphate compound.Suitable metal dialkyl phosphorodithioate can comprise dialkyl phosphorodithioate metal-salt, and wherein metal can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel, copper or zinc.
Dialkyl phosphorodithioate metal-salt can be prepared according to known technology, usually by one or more alcohol or phenol and P 2s 5reaction, first forms dialkyldisulfide for phosphoric acid (DDPA), uses in metallic compound subsequently and the DDPA formed.Such as, by the mixture reaction of primary alconol and secondary alcohol, phosphorodithioic acid can be prepared.Or, when the alkyl on a kind of alcohol is entirely secondary characteristic, and when the alkyl on other alcohol is entirely Bert, multiple phosphorodithioic acid can be prepared.In order to prepare metal-salt, any alkalescence or neutral metal compound can be used, but the most usually adopt oxide compound, oxyhydroxide and carbonate.Owing to using excessive alkaline metal cpds in neutralization reaction, commercial additive is usually containing excessive metal.
Dialkyldisulfide, and to can be represented by the formula for dialkyldisulfide is for the oil soluble salt of phosphoric acid for zinc phosphate (ZDDP):
Wherein R and R' can be the identical or different alkyl containing 1-18 (such as 2-12) carbon atom, and comprises various group, such as alkyl, thiazolinyl, aryl, arylalkyl, alkaryl and alicyclic group.R and R' group can be the alkyl of 2-8 carbon atom.Therefore, group can be such as ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.In order to obtain oily solubleness, in phosphorodithioic acid, the sum (that is, R and R') of carbon atom is generally about 5 or larger.Therefore dialkyldisulfide can comprise zinc dialkyl dithiophosphate for zinc phosphate.
Can be used as comprising any suitable organo phosphorous compounds, such as but not limited to phosphoric acid ester, thiophosphatephosphorothioate, phosphorodithioate, phosphorous acid ester and salt thereof and phosphonic acid ester based on other suitable component of the wear preventative of phosphorus.Suitable example is Tritolyl Phosphate (TCP), dialkyl phosphite (such as, hydrogen dibutyl phosphite) and valeric acid phosphoric acid ester.
Another kind of suitable component is the succinimide of phosphorylated, the succinic acylating agent such as replaced at alkyl and and phosphorus source (such as inorganic or organic phosphoric acid or ester) polyamine of combining between the complete reaction product of reaction.In addition, it can comprise following compound: wherein except deriving from the imide bond of the type of the reaction of primary amino and anhydride moiety, product also can have acid amides, amidine and/or sat linkage.
Wear preventative based on phosphorus can be enough to provide the amount of about 200-about 2000 ppm phosphorus to be present in lubricating composition.As another example, the wear preventative based on phosphorus can be enough to provide the amount of about 500-about 800 ppm phosphorus to be present in lubricating composition.
Wear preventative based on phosphorus can a certain amount ofly be present in lubricating composition, and it is enough to provide the basic metal of about 1.6-about 3.0 (ppm/ppm) and/or alkaline earth metal content (ppm) (total amount based on basic metal in lubricating composition and/or the alkaline-earth metal) ratio with phosphorus content (ppm) (total amount based on phosphorus in lubricating composition).
friction modifiers
Embodiment of the present disclosure can comprise one or more friction modifiers.Suitable friction modifiers can comprise containing metal and metal-free friction modifiers, and can include but not limited to tetrahydroglyoxaline, acid amides, amine, succinimide, oxyalkylated amine, oxyalkylated ether amine, amine oxide, amidoamines, nitrile, betaine, quaternary amine, imines, amine salt, aminoguanidine, alkanolamide, phosphonate, compound, glyceryl ester etc. containing metal.
Suitable friction modifiers can containing the alkyl being selected from straight chain, side chain or aromatic hydrocarbyl or their mixture, and can be saturated or undersaturated.Alkyl can be made up of carbon and hydrogen or heteroatoms (such as sulphur or oxygen).Alkyl can be saturated or undersaturated in the scope of about 12-about 25 carbon atoms.
Amine friction modifiers can comprise the acid amides of polyamine.Such compound can have saturated or undersaturated straight-chain alkyl or their mixture, and can containing 12-about 25 carbon atoms of having an appointment.
Other example of suitable friction modifiers comprises oxyalkylated amine and oxyalkylated ether amine.Such compound can have saturated or undersaturated straight-chain alkyl or their mixture.They can containing 12-about 25 carbon atoms of having an appointment.Example comprises the amine of ethoxylation and the ether amine of ethoxylation.
Amine and acid amides can former state use or be with boron compound (such as boron oxide, halo boron, metaborate, boric acid or singly-, two-or trialkylborates) adducts or reaction product form.Other suitable friction modifiers is described in US 6,300,291, and it is incorporated herein by reference.
Other suitable friction modifiers can comprise organic, ashless (metal-free), unazotized organic friction modifiers.Such friction modifiers can comprise and reacts by carboxylic acid and acid anhydrides and alkanol the ester formed.Other available friction modifiers generally includes and the polar terminal group of lipophilic hydrocarbon chain covalent bonding (such as, carboxyl or hydroxyl).The ester of carboxylic acid and acid anhydrides and alkanol is described in U.S. 4,702,850.Another example of organic ashless unazotized friction modifiers is commonly referred to glyceryl monooleate (GMO), and it can contain monoesters and the diester of oleic acid.Other suitable friction modifiers is described in U.S. Patent number 6,723,685, and it is incorporated herein by reference.Ashless friction properties-correcting agent can be present in lubricant compositions, based on the gross weight of lubricant compositions in the amount of about 0.1-about 0.4 % by weight scope.
Suitable friction modifiers also can comprise one or more molybdenum compounds.Molybdenum compound can be selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate, dithiophosphinic acids molybdenum, xanthogenic acid molybdenum, Thioxanthate molybdenum, moly-sulfide, three core organic molybdenums, molybdenum/amine compound and their mixture.
In addition, molybdenum compound can be acid molybdenum compound.Comprise molybdic acid, ammonium molybdate, Sodium orthomolybdate, potassium molybdate and other alkali metal molybdate and other molybdenum salt, such as, molybdic acid hydrogen sodium, MoOCl 4, MoO 2br 2, Mo 2o 3cl 6, molybdic oxide or similar acid molybdenum compound.Such as, or composition provides molybdenum by the molybdenum/sulfur compound of basic nitrogen compound, as being described in U.S. Patent number 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; With WO 94/06897.
Suitable molybdenum dithiocarbamate can be represented by the formula:
Wherein R 1, R 2, R 3and R 4represent hydrogen atom, C independently of one another 1-C 20alkyl, C 6-C 20cycloalkyl, aryl, alkylaryl or aralkyl or the C containing ester, ether, alcohol or carboxyl 3-C 20alkyl; And X 1, X 2, Y 1and Y 2represent sulphur or Sauerstoffatom independently of one another.
For each R 1, R 2, R 3and R 4, the example of suitable group comprises 2-ethylhexyl, nonyl phenyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, sub-oil base, cyclohexyl and phenyl methyl.R 1-R 4c can be had separately 6-C 18alkyl.X 1and X 2can be identical, and Y 1and Y 2can be identical.X 1and X 2both all can comprise sulphur atom, and Y 1and Y 2both all can comprise Sauerstoffatom.
Other example of molybdenum dithiocarbamate comprises C 6-C 18dialkyl group or diaryldithiophosphate carbaminate or alkyl-aryl-group dithiocar-bamate, such as dibutyl-, diamyl-two-(2-ethyl hexyl)-, dilauryl-, two oleyls-and dicyclohexyl-dithiocar-bamate.
Another kind of suitable organic-molybdenum compound is three core molybdenum compound, such as formula Mo 3s kl nq zthose and their mixture, wherein L represents the part that the independence of the organic group of the carbon atom with sufficient amount is selected, to make compound being soluble or to dispersible in oil, n is 1-4, k changes at 4-7, and Q is selected from neutral supplied for electronic compound, such as water, amine, alcohol, phosphine and ether, z in 0-5 scope, and comprises nonstoichiometry value.In the organic group of all parts, at least 21 carbon atoms altogether can be there are, such as at least 25, at least 30 or at least 35 carbon atoms.Suitable molybdenum compound is in addition described in US 6,723,685, and it is incorporated herein by reference.
Molybdenum compound can provide the amount of about 5 ppm-500 ppm weight molybdenums to be present in the engine lubricant prepared completely.As another example, molybdenum compound can provide the amount of about 50-300 ppm weight molybdenum to exist.The specially suitable amount of molybdenum compound can be the amount being enough to provide about 60-about 250 ppm weight molybdenum to lubricant compositions.
defoamer
In some embodiments, suds suppressor can form another component being applicable to composition.Suds suppressor can be selected from silicone, polyacrylic ester etc.In engine lubrication agent formulation described herein, the amount of defoamer can in about 0.001 % by weight-Yue 0.1 % by weight scope, based on the gross weight of preparation.As another example, defoamer can about 0.004 % by weight-Yue 0.008 % by weight amount exist.
oxidation retarder component
Oxidation retarder or antioxidant reduce the operationally deteriorated trend of basic material, and described deterioration proves by oxidation products, the sludge such as deposited on the metal surface and clear lacquer deposit, and are proved by the viscosity growth of finished lubricants.Such oxidation retarder comprise hindered phenol, sulfuration hindered phenol, there is C 5-C 12the alkaline earth salt of the alkylphenol monothioester of alkyl group side chain, the alkylphenol of sulfuration, sulfuration or unvulcanised alkylphenol metallic salts as the phenolate of nonylphenol sulfurated lime, ashless oil soluble phenolate and sulfuration, phosphoric acid sulfuration or the hydrocarbon of sulfuration, phosphide, metal thiocarbamates and oil-soluble copper compounds, as at U.S. Patent number 4,867, describe in 890.
Other antioxidant spendable comprises space hindered phenol and ester thereof, diarylamine, alkylating thiodiphenylamine, the compound of sulfuration and ashless dialkyl dithio amino formate.The limiting examples of space hindered phenol includes but not limited to 2,6 di t butyl phenol, 2,6-di-t-butyl methylphenol, 4-ethyl-2,6 di t butyl phenol, 4-propyl group-2,6 di t butyl phenol, 4-butyl-2,6 di t butyl phenol, 4-amyl group-2,6 di t butyl phenol, 4-hexyl-2,6 di t butyl phenol, 4-heptyl-2,6 di t butyl phenol, 4-(2-ethylhexyl)-2,6 di t butyl phenol, 4-octyl group-2,6 di t butyl phenol, 4-nonyl-2,6 di t butyl phenol, 4-decyl-2,6 di t butyl phenol, 4-undecyl-2,6 di t butyl phenol, 4-dodecyl-2,6 di t butyl phenol, methylene-bridged space hindered phenol includes but not limited to 4,4-methylene-bis (6-tert-butyl o-cresol), 4,4-methylene-bis (2-tert-pentyl-ortho-cresol), 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 4,4-methylene radical-bis-(2,6 di t butyl phenol) and their mixture, as described in U.S. Publication No 2004/0266630.
Diarylamine antioxidant includes but not limited to the diarylamine with following formula:
Wherein R ' and R ' ' is independent separately represents the substituted or unsubstituted aryl with 6-30 carbon atom.Substituent illustrative example for aryl comprises aliphatic hydrocarbyl (such as having the alkyl of 1-30 carbon atom), hydroxyl, halogen group, carboxylic acid or ester group or nitro.
Preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or two aryl are had 4-30 carbon atom by least one to aryl, preferred 4-18 carbon atom, the most preferably alkyl of 4-9 carbon atom replace.Preferably one or two aryl is substituted, such as, and the mixture of list-alkylating diphenylamine, two-alkylating diphenylamine or singly-and two-alkylating diphenylamine.
Diarylamine can be the structure in the molecule containing more than one nitrogen-atoms.Therefore, diarylamine can contain at least two nitrogen-atoms, and wherein at least one nitrogen-atoms has two aryl be attached thereto, such as, a nitrogen-atoms has the different diamines of secondary nitrogen-atoms and two aryl.
The example of spendable diarylamine includes but not limited to: diphenylamine; Various alkylating diphenylamine; 3-hydroxy diphenyl amine; N-phenyl-1,2-phenylenediamine; N-phenyl-Isosorbide-5-Nitrae-phenylenediamine; Monobutyl diphenylamine; Dibutyl diphenylamine; Single octyldiphenylamine; Dioctyl diphenyl amine; Single nonyl diphenylamine; Dinonyldiphenylamine; Single tetradecyl diphenyl amine; Two (tetradecyl) diphenylamine; Phenyl-α-naphthylamine; Single octyl phenyl-Alpha-Naphthyl amine; Phenyl-β-naphthylamine; Single heptyl diphenylamine; Diheptyl-diphenylamine; The diphenylamine of the styrol of para-orientation; Butyl octyl two-the phenyl amine of mixing; With the octyl styrene base diphenylamine of mixing.
Sulphur-containing antioxidant includes but not limited to the alkene of sulfuration, it is characterized by the type of the alkene of the production for them and the final sulphur content of antioxidant.Preferred high molecular weight olefin, that is, molecular-weight average is those alkene of 168-351 g/mol.The example of spendable alkene comprises alpha-olefin, isomerized alpha-olefin, branched olefin, cyclic olefin and these combination.
Alpha-olefin includes but not limited to any C 4-C 25alpha-olefin.Before vulcanization reaction or during vulcanization reaction, alpha-olefin can be isomerized.Also can use structure and/or the conformer of the alpha-olefin containing internal double bonds and/or branch.Such as, iso-butylene is the branched olefin counterpart of alpha-olefin 1-butylene.
The sulphur source that can be used for the vulcanization reaction of alkene comprises: elementary sulfur, monochlorinated sulphur, sulfur dichloride, sodium sulphite, sodium polysulphide and these mixture that is common or that add in the different steps of sulfidation.
Because their degree of unsaturation, unsaturated oil also can cure and be used as antioxidant.The example of spendable oil or fat comprises Semen Maydis oil, Canola Oil, Oleum Gossypii semen, wine stone oil, sweet oil, plam oil, peanut oil, cocounut oil, rapeseed oil, safflower oil, sesame seed oil, soybean oil, wunflower seed oil, butter and these combination.
The amount being delivered to the alkene of the sulfuration of finished lubricants or the fatty oil of sulfuration is based on the alkene of sulfuration or the sulphur content of fatty oil and the expectation content of sulphur that will be delivered to finished lubricants.Such as, when joining finished lubricants with 1.0 % by weight processing horizontals, the fatty oil of the sulfuration containing 20 % by weight sulphur or alkene will send the sulphur of 2000 ppm to finished lubricants.When joining finished lubricants with 1.0 % by weight processing horizontals, the fatty oil of the sulfuration containing 10 % by weight sulphur or alkene will send the sulphur of 1000 ppm to finished lubricants.Expect that the alkene of sulfuration or the fatty oil of sulfuration send 200 ppm-2000 ppm sulphur to finished lubricants.
Usually, suitable engine lubricant can comprise the binder component of following listed scope.
Table 2
Component % by weight (wide) % by weight (typically)
Dispersion agent (reaction product of component A, B, C and D) 0.5-10.0 1.0-5.0
Other dispersion agent 0-10% 1.0-6.0%
Antioxidant 0-5.0 0.01-3.0
Metal detergent 0.1-15.0 0.2-8.0
Inhibiter 0-5.0 0-2.0
Metal dialkyl phosphorodithioate 0.1-6.0 0.5-4.0
Ashless amine phosphate ester salt 0-6.0 0.0-4.0
Defoamer 0-5.0 0.001-0.15
Anti-wear agent 0-1.0 0-0.8
Pour point reducer 0.01-5.0 0.01-1.5
Viscosity modifier 0.01-20.00 0.25-10.0
Friction modifiers 0-2.0 0.1-1.0
Base oil Surplus Surplus
Amount to 100 100
The other optional additives that can be included in lubricant compositions described herein includes but not limited to rust-preventive agent, emulsifying agent, emulsion splitter and oil soluble Ti-containing additive.
Additive for preparing composition described herein can be blended in base oil separately or with various sub-portfolio.But, can be applicable to using multifunctional additive for lubricating oils (that is, additive adds thinner, such as hydrocarbon solvent) blended all components simultaneously.When adopting multifunctional additive for lubricating oils form, use multifunctional additive for lubricating oils can utilize the mutual consistency provided by the combination of composition.In addition, enriched material is used can to reduce the blended time and the possibility of blended error can be reduced.
The disclosure provides new lubricating oil blend, and especially preparation is used as automotive engine lubrication agent.Embodiment of the present disclosure can provide the lubricating oil being applicable to engine application, and it is provided in the improvement in one or more following characteristics: oxidation-resistance, wear resistance, rust inhibition, fuel economy, water tolerance, entrained air, seal protection and foam reduce character.
In order to prove benefit and the advantage of lubricant compositions of the present disclosure, provide following non-limiting example.Dispersion agent (c) is prepared according to following examples.
Embodiment 1
Device needs the 1 L 4-neck flask with agitator, feed hopper, temp probe, temperature regulator, heating jacket, water trap and condenser.Flask loads 2100 M npolyisobutenyl succinic anhydride (PIBSA) (195.0 g; 0.135 mole), and be heated to 160 DEG C under nitrogen blanket.Polyvinylamine mixture (21.17 g are dropwise added through 30 minutes; 0.112 mole).Reaction mixture is stirred 4 hours, subsequently coupling vacuum stripping 1 hour under 711 mm Hg.(172.0 g), mixture is stirred 15 minutes to add technical oil.At 160 DEG C, portion adds 1,8-naphthalic anhydride (13.39 g; 0.068 mole).Reaction mixture is heated to 165 DEG C, stirs 4 hours.Apply vacuum (711 mm Hg) and reach 1 hour, to remove the water of any remnants.Reaction product, through the pressure filtration of Hiflow Super Cel Celite diatomite, obtains 364 g dark brown viscous liquid (% N, 1.75; TBN, 36.0).
500 mL flasks load previous reaction product (200.0 g; 0.102 mole), and be heated to 160 DEG C under nitrogen blanket.Portion adds maleic anhydride (4.48 g; 0.045 mole).Reaction mixture is allowed to stir 4 hours, subsequently coupling vacuum stripping 1 hour under 711 mm Hg.(4.48 g), mixture is stirred 15 minutes to add process oil.Reaction product, through the pressure filtration of Hiflow Super Cel Celite diatomite, obtains 165 g dark brown viscous liquid (% N, 1.67; TBN, 24.1).
The test of evaluation sediment monitoring and stability of emulsion
In order to evaluate lubricant formulations of the present disclosure, in Sequence IIIG Engine Block Test, testing various disperser composition reduce the ability of engine deposits and keep the ability of stable emulsion in the presence of water.In the examples below, use following dispersion agent: dispersion agent 1 is conventional boronation succinimide dispersants, and number-average molecular weight is about 1000-about 1400 dalton; Nitrogen content is about 1.5-about 1.7 % by weight; Dispersion agent 2 is above-mentioned dispersion agent (c), and number-average molecular weight is greater than 1800 dalton, and nitrogen content is about 1.17 % by weight; With the succinimide dispersants that dispersion agent 3 is conventional, number-average molecular weight is 2100 dalton, and nitrogen content is about 1.58 % by weight; Dispersion agent 4 is conventional succinimide dispersants, and number-average molecular weight is about 1300 dalton, and nitrogen content is about 1.8 % by weight.The weight percentage of the dispersion agent in table is based on activeconstituents.Antioxidant 1 (Antiox. 1) is conventional diphenylamine antioxidant; Antioxidant 2 (Antiox. 2) is the alkene antioxidant of conventional sulfuration; Antioxidant 3 (Antiox. 3) is conventional phenols type antioxidant; With the molybdenum amine complex that molybdenum additives is conventional, and press the display of ppm weight metal molybdenum.Measure piston deposit (WPD) the index grade of weighing according to Sequence IIIG Engine Block Test, and at 25 DEG C, measure stability of emulsion according to E85 emulsion test (ASTM D7563).Result is shown in following table.
Table 3
As shown in aforementioned result, compared with the disperser composition of embodiment 1-8, in Sequence IIIG Engine Block Test, the lubricant compositions of embodiment 9-12 not only presents excellent performance, and under higher molybdenum additives treatment rate, the lubricant compositions of embodiment 9-12 also presents the stability of emulsion of improvement.By contrast, embodiment 15 and 16 is containing the combination of non-boronation succinimide dispersants (replacing the dispersion agent of boronation) with dispersion agent 2.When using the dispersion agent of dispersion agent 2 and non-boronation, lubricant compositions is not by using the emulsion of 295 ppm molybdenums to test.By embodiment 13 and 14, obviously, for mixture of dispersing agents, the upper limit of molybdenum treatment rate is about 300 ppm molybdenums.Exceed about 300 ppm molybdenums (embodiment 14), lubricant compositions failure in emulsion test.
In numerous places of whole specification sheets, quote multiple United States Patent (USP).All these files quoted clearly all are incorporated to the disclosure, as complete description in this article.
Consider the practice of specification sheets and embodiment disclosed herein, other embodiment of the present disclosure it will be apparent to those skilled in the art that.One or more than one can be referred to whole " " used in the specification and claims.Unless otherwise indicated, otherwise all numerals of the amount of the statement composition used in the specification and in the claims, character (such as molecular weight, percentage ratio, ratio), reaction conditions etc. be interpreted as in all cases by term " about " modify.Therefore, unless contrary situation is described, otherwise the digital parameters described in the specification and in the claims is approximation, and it can be sought the character of the expectation obtained according to the present invention and change.On minimum level, and be not will attempt to limit doctrine of equivalents to be applied to the scope of claim, each digital parameters should at least according to the significant digit of report and the numeral obtained by applying the common technology of rounding up explain.Although the digital scope and the parameter that describe wide region of the present invention are approximation, the numerical value described in the particular embodiment is as far as possible accurately reported.But any numerical value is inherently containing some error that must be obtained by the standard deviation existed in their corresponding thermometricallies.Expection specification sheets and embodiment only regard exemplary as, and the true scope and spirit of the invention is indicated by following claim.
In practice, foregoing embodiments is subject to the impact of noticeable change.Therefore, embodiment is not intended to be limited to the particular instantiation stated above.But, foregoing embodiments in the spirit and scope of claims, comprise its legally can Equivalent.
Patentee is not intended to any disclosed embodiment to contribute to the public, and may not fall on literal in any disclosed amendment or change in the degree in the scope of claim, under the doctrine of equivalents, thinks that they are parts of the present invention.

Claims (10)

1. a lubricant additive compositions, described composition comprises:
A () contributes about 20 to the organic molybdenum being not more than 300 ppm weight molybdenums, based on the gross weight of the lubricant compositions containing compositions of additives to lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
2. the compositions of additives of claim 1, wherein component (iii) comprises 1,8-naphthalic anhydride.
3. the compositions of additives of claim 1, wherein the hydrocarbyl substituent of component (b) is derived from the polyolefine of number-average molecular weight in about 1000-about 1600 dalton's scope, passes through gel permeation chromatography.
4. the compositions of additives of claim 1, wherein every molar constituent (ii) is had an appointment the fused aromatic compounds reaction of 0.25-about 1.5 moles.
5. the compositions of additives of claim 1, the lubricant compositions wherein containing additive comprises component (b) and (c) of about 0.5-about 5 % by weight.
6. the compositions of additives of claim 1, wherein component (i) comprises polyisobutenyl succinic acid or acid anhydrides, and component (iii) comprises 1,8-naphthalic anhydride, and component (iv) comprises maleic anhydride.
7. the compositions of additives of claim 1, wherein every molar constituent (ii) is had an appointment component (iv) reaction of 0.25-about 1.5 moles.
8. a lubricant compositions, described composition comprises the compositions of additives of claim 1.
9. within the engine control piston deposition method, described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and lubricant additive compositions with lubricant viscosity, and described lubricant additive compositions comprises:
(a) to described lubricant compositions contribution about 20 to the organic molybdenum of molybdenum being not more than 300 ppm weight, based on the gross weight of described lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
10. one kind for keeping the method for the stability of emulsion of engine lubricant compositions, described method comprises makes lubricant compositions lubricating engine, described lubricant compositions comprises the base oil and lubricant additive compositions with lubricant viscosity, and described lubricant additive compositions comprises:
(a) to described lubricant compositions contribution about 20 to the organic molybdenum of molybdenum being not more than 300 ppm weight, based on the gross weight of described lubricant compositions;
The Hydrocarbyl-substituted succinic imide dispersion agent of (b) boronation; With
The reaction product of (c) (i) alkyl-dicarboxylic acid or acid anhydrides, (ii) polyamine, (iii) fused aromatic compounds containing dicarboxyl and (iv) non-aromatic dicarboxylic acid or acid anhydrides, wherein the number-average molecular weight of the alkyl of alkyl-dicarboxylic acid or acid anhydrides is greater than 1800 dalton, passes through gel permeation chromatography;
Wherein (b) and the weight ratio of (c) are in about 1:1 extremely about 4:1 scope.
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